EP4155330A1 - Procédé pour la préparation d'un polymère adhésif sensible à la pression dispersé - Google Patents

Procédé pour la préparation d'un polymère adhésif sensible à la pression dispersé Download PDF

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Publication number
EP4155330A1
EP4155330A1 EP22195431.6A EP22195431A EP4155330A1 EP 4155330 A1 EP4155330 A1 EP 4155330A1 EP 22195431 A EP22195431 A EP 22195431A EP 4155330 A1 EP4155330 A1 EP 4155330A1
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EP
European Patent Office
Prior art keywords
monomers
weight
acrylate
sum
sensitive adhesive
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EP22195431.6A
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German (de)
English (en)
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Karl-Heinz Schuhmacher
Saskia Groeer
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BASF SE
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BASF SE
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Priority to EP22195431.6A priority Critical patent/EP4155330A1/fr
Publication of EP4155330A1 publication Critical patent/EP4155330A1/fr
Priority to PCT/EP2023/074434 priority patent/WO2024056484A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate

Definitions

  • the invention relates to pressure-sensitive adhesive compositions in the form of an aqueous polymer dispersion comprising a dispersed pressure-sensitive adhesive polymer formed by emulsion polymerization of 2-octyl acrylate, styrene, a hydroxyalkyl acrylate and monomers having at least one acid group and optionally further monomers.
  • the pressure-sensitive adhesive composition may be used to produce self-adhesive articles such as self-adhesive labels, self-adhesive tapes or self-adhesive films.
  • Aqueous pressure-sensitive adhesives are characterized by their adhesion-cohesion balance. Improved adhesion/cohesion balance is applicable in most pressure-sensitive adhesive applications and in particular for self-adhesive labels. For label applications high tack is desired to ensure high labelling line speeds while the adhesive needs to provide sufficient cohesion for good convertibility Typically one of these properties cannot be increased without reducing the other property. Another need for aqueous pressure-sensitive adhesives is a reduced carbon-footprint. Although this can be achieved by using partially or completely biobased monomers for producing adhesive polymers, the adhesion/cohesion balance requirement should be also met by the adhesive polymers based at least in part on bio-based monomers.
  • WO 2009/129087 describes the use of 2-octyl (meth)acrylates in adhesive compositions.
  • WO 00/68335 describes contact bonding adhesives containing an aqueous polymer dispersion which is characterized in that the polymer is made from C1 to C12 alkyl(meth)acrylates, vinylaromatic compounds, ethylenically unsaturated hydroxy compounds and optionally further monomers.
  • US 2020/0017725 A1 describes pressure-sensitive adhesive compositions comprising the emulsion polymerization product of a monomer mixture comprising an alkyl ester of (meth)acrylic acid, a vinyl aromatic monomer, a hydroxyl functional (meth)acrylate monomer and an ureido substituted monomer and optional further monomers.
  • the present invention provides pressure-sensitive adhesive compositions in the form of aqueous polymer dispersions comprising at least one dispersed pressure-sensitive adhesive polymer formed by emulsion polymerization of
  • a pressure-sensitive adhesive is a viscoelastic adhesive which sets to form a film that at room temperature (20°C) remains permanently tacky and adhesive in the dry state. Adhesion to substrates is affected immediately by gentle pressure.
  • aqueous polymer dispersion and “aqueous solvent” refers to solvent systems primarily based on water, preferably containing no or less than 10%, less than 5% or less than 1% by weight of organic solvents, based on the total composition.
  • the glass transition temperature is determined by differential scanning calorimetry as the midpoint temperature when evaluating the second heating curve at a heating rate of 20 K/min (ASTM D 3418-08).
  • the pressure-sensitive adhesive polymer is produced from 2-octyl acrylate.
  • the amount of 2-octyl acrylate monomer (i) is from 10 to 95% by weight, preferably from 40 to 95% by weight, or from 50 to 95% by weight, or from 40 to less than 90% by weight, or from 60 to less than 90% by weight, based on the sum of all monomers.
  • the 2-octyl acrylate is bio-based, wherein the acrylic acid component or the 2-octyl component or both are bio-based.
  • at least 50 wt.%, more preferred 100 wt.% of 2-octyl acrylate monomer (i) is made from bio-based 2-octanol and non-bio-based or bio-based acrylic acid, i.e. preferably at least the carbon atoms of the 2-octyl group of 2-octyl acrylate (i) are of biological origin.
  • Monomer (ii) styrene is used in an amount of from 0.1 to 5% by weight, preferably from 0.5 to 5% by weight, or from 1 to 5% by weight, or from 1 to 2% by weight, based on the sum of all monomers.
  • the pressure-sensitive adhesive polymer is produced from at least one monomer (iii), which is a hydroxyalkyl (meth)acrylate.
  • This monomer is an hydroxyalkyl ester of (meth)acrylic acid with at least one hydroxy group in the hydroxyalkyl group.
  • the amount of functional monomer (iii) is from 0.1 to 5% by weight, preferably from 0.5 to 5% by weight, or from 1 to 3% by weight, based on the sum of all monomers.
  • Suitable hydroxyl functional (meth)acrylate monomers (iii) are C 1 -C 10 -hydroxyalkyl (meth)acrylates which have 1-10 carbon atoms in the hydroxyalkyl group.
  • Preferred examples are hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxybutyl acrylate. Most preferred is hydroxypropyl acrylate (including mixtures of isomers such as 2-hydroxy-propyl acrylate and 2-hydroxy-1-methylethyl acrylate).
  • the pressure-sensitive adhesive polymer is produced from monomers (iv) having at least one acid group.
  • the amount of monomers (iv) having at least one acid group is from 0.1% to 10% by weight, preferably from 0.2% to 8% by weight, more preferably from 0.5% to 5% by weight, based on the sum of all monomers.
  • Monomers (iv) are monomers having at least one acid group (acid monomers), i.e. ethylenically unsaturated acids or ethylenically unsaturated acid anhydrides, and are polymerizable by free-radical polymerization.
  • Suitable acid monomers are, for example, ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids and vinylphosphonic acid.
  • ethylenically unsaturated carboxylic acids are alpha,beta-monoethylenically unsaturated mono- and dicarboxylic acids comprising 3 to 6 carbon atoms in the molecule. Examples thereof are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid and vinyllactic acid.
  • Suitable ethylenically unsaturated sulfonic acids include vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropane sulfonic acid, sulfopropyl acrylate and sulfopropyl methacrylate.
  • Acrylic acid, methacrylic acid, itaconic acid and mixtures thereof are preferred and acrylic acid is particularly preferred.
  • the pressure-sensitive adhesive polymer is produced from 1-octyl acrylate in an amount of from 0 to 70% by weight, preferably from 0 to 50% by weight or from 0 to 30% by weight, or from 1 to 30% by weight, based on the sum of all monomers.
  • the 1-octyl acrylate is bio-based, wherein the acrylic acid component or the 1-octyl component or both are bio-based.
  • Preferred is partly bio-based 1-octyl acrylate which is an ester of non-bio-based acrylic acid and bio-based 1-octanol or fully bio-based 1-octyl acrylate which is an ester of bio-based acrylic acid and bio-based 1-octanol.
  • At least 50 wt.%, more preferred 100 wt.% of 1-octyl acrylate monomer is made from bio-based 1-octanol and non-bio-based or bio-based acrylic acid, i.e. preferably at least the carbon atoms of the 1-octyl group of 1-octyl acrylate are of biological origin.
  • the pressure-sensitive adhesive polymer is produced from isobutyl acrylate in an amount of from 0 to 40% by weight, preferably from 0 to 20% by weight or from 0 to 10% by weight, or from 1 to 10% by weight, based on the sum of all monomers.
  • the isobutyl acrylate is bio-based, wherein the acrylic acid component or the isobutyl component or both are bio-based.
  • Preferred is partly bio-based isobutyl acrylate which is an ester of non-bio-based acrylic acid and bio-based isobutanol or fully bio-based isobutyl acrylate which is an ester of bio-based acrylic acid and bio-based isobutanol.
  • At least 50 wt.%, more preferred 100 wt.% of isobutyl acrylate monomer is made from bio-based isobutanol and non-bio-based or bio-based acrylic acid, i.e. preferably at least the carbon atoms of the isobutyl group of isobutyl acrylate are of biological origin.
  • the pressure-sensitive adhesive polymer is produced from ethyl acrylate in an amount of from 0 to 70% by weight, preferably from 0 to 40% by weight, or from 1 to 40% by weight, or from 5 to 30% by weight, based on the sum of all monomers.
  • the ethyl acrylate is bio-based, wherein the acrylic acid component or the ethyl component or both are bio-based.
  • Preferred is partly bio-based ethyl acrylate which is an ester of non-bio-based acrylic acid and bio-based ethanol or fully bio-based ethyl acrylate which is an ester of bio-based acrylic acid and bio-based ethanol.
  • At least 50 wt.%, more preferred 100 wt.% of ethyl acrylate monomer is made from bio-based ethanol and non-bio-based or bio-based acrylic acid, i.e. preferably at least the carbon atoms of the ethyl group of ethyl acrylate are of biological origin.
  • the pressure-sensitive adhesive polymer is produced from 2-ethylhexyl acrylate in an amount of from 0 to 60% by weight, preferably from 1 to 40% by weight or from 2 to 20% by weight, based on the sum of all monomers.
  • the pressure-sensitive adhesive polymer is produced from of methyl (meth)acrylate in an amount of from 0 to 20% by weight, preferably from 0 to 15% by weight, or from 1 to 20% by weight or from 2 to 15%, or from 2 to 10% by weight, based on the sum of all monomers.
  • the pressure-sensitive adhesive polymer is produced from vinyl acetate in an amount of from 0 to 10% by weight, preferably from 0 to 8%, or from 1 to 8% by weight, based on the sum of all monomers.
  • the pressure-sensitive adhesive polymer is optionally produced from at least one monomer (xi) which is a (meth)acrylate alkyl ester monomer different from monomers (i) and (v) to (viii) and having, when polymerized as a homopolymer, a glass transition temperature of less than -20 °C (so-called "soft" monomer).
  • the amount of soft (meth)acrylic ester monomer (xi) is preferably from 0 to 30% by weight, preferably from 1% to 30% by weight or from 2 to 25% by weight, or from 3 to 20% by weight, based on the sum of all monomers.
  • the soft monomers (xi) are preferably selected from acrylic esters, in particular from C 3 - to C 10 -alkyl acrylates, or from C 4 - to C 8 -alkyl acrylates. Suitable examples include n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, n- heptyl acrylate, and isooctyl acrylate (2-methylheptyl acrylate) and also mixtures of these monomers.
  • the pressure-sensitive adhesive polymer is optionally produced from at least one functional monomer (xii) selected from hydroxyl functional (meth)acrylate monomers different from (iii) and ureido substituted ethylenically unsaturated monomers.
  • the amounts of monomers (xii) are preferably from 0 to 10% by weight, or from 0,1 to 10% by weight, or from 0.5 to 7% by weight, based on the sum of all monomers.
  • hydroxyl functional (meth)acrylate monomers different from (iii) are N-alkylol-(meth)acrylamides such as N-methylol(meth)acrylamide.
  • Preferred amounts of hydroxyl functional (meth)acrylate monomers different from (iii) are 0 to 5% by weight, or 0.5 to 5 % by weight based on the sum of all monomers.
  • the ureido substituted ethylenically unsaturated monomer has at least one ethylenically unsaturated, radically polymerizable group and at least one functional group selected from ureido groups.
  • Suitable ureido substituted ethylenically unsaturated monomers are monomers selected from the group consisting of (meth)acrylate monomers having a substituent of the formula where X is NH or NR, and R is a C1 to C4 alkyl group and the arrow at the N-atom denotes the linkage point of the substituent to the (meth)acrylate monomer.
  • Suitable ureido substituted ethylenically unsaturated monomers are, for example, those of the formula where X is as defined above, R is hydrogen or methyl, and A is a divalent linking group, preferably a C1 to C10 alkyl group or a C2 to C4 alkyl group. Particular preference is given to using ureidoalkyl (meth)acrylates having 1 to 10 C atoms, preferably 2 to 4 C atoms in the alkyl group, Most preferred is ureidoethyl methacrylate (2-(2-oxoimidazolidin-1-yl)ethyl methacrylate; also identified as ureido methacrylate or abbreviated as UMA).
  • Preferred amounts of ureido substituted ethylenically unsaturated monomers are from 0,05 to 2% by weight, more preferred from 0.1 to 2% by weight, or from 0,1 to 1% by weight, based on the sum of all monomers.
  • the pressure-sensitive adhesive polymer is optionally produced from at least one monomer, which is different from monomers (i) to (xii).
  • the monomers are copolymerizable, ethylenically unsaturated compounds.
  • the amount of monomers (xii) is preferably from 0 to 10% by weight or from 0 to 5% by weight, based on the sum of all monomers.
  • Monomers are for example selected from vinyl esters of carboxylic acids comprising up to 20 carbon atoms different from vinyl acetate, vinylaromatics different from styrene and having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols comprising 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds and (meth)acrylamides or mixtures of these monomers.
  • Further monomers additionally include phenyloxyethyl glycol mono(meth)acrylate, glycidyl (meth)acrylate, aminoalkyl (meth)acrylates, for example 2-aminoethyl (meth)acrylate.
  • Alkyl groups preferably have from 1 to 20 carbon atoms.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are for example vinyl laurate, vinyl stearate, vinyl propionate and vinyl versatate.
  • Vinylaromatic compounds include vinyltoluene, alpha- and p-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are ethylenically unsaturated compounds substituted by chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers include vinyl methyl ether or vinyl isobutyl ether. Preference is given to vinyl ethers of alcohols comprising 1 to 4 carbon atoms. Suitable hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds are, for example, butadiene, isoprene and chloroprene.
  • a preferred pressure-sensitive adhesive composition comprises at least one pressure-sensitive adhesive polymer formed by emulsion polymerization of
  • a preferred pressure-sensitive adhesive composition comprises at least one pressure-sensitive adhesive polymer formed by emulsion polymerization of
  • a preferred pressure-sensitive adhesive composition comprises at least one pressure-sensitive adhesive polymer formed by emulsion polymerization of
  • bio-based materials are used for producing the pressure-sensitive adhesive polymer, which preferably is partly or completely made of partly or fully bio-based monomers.
  • Bio-based materials are materials which are made from a renewable source and have a smaller impact on the environment. They do not require all the refining steps required for petroleum-based products, which are very expensive in terms of energy. The production of CO 2 is reduced such that bio-based materials contribute less to global warming.
  • bio-based indicates that the material is of biological origin and comes from biomaterial and renewable resources.
  • a material of renewable origin or biomaterial is an organic material wherein the carbon comes from the CO 2 fixed recently (on a human scale) by photosynthesis from the atmosphere.
  • a biomaterial (carbon of 100% natural origin) has an isotopic ratio 14 C/ 12 C greater than 10 -12 , typically about 1.2 ⁇ 10 -12 , while a fossil material has a zero ratio.
  • the isotopic 14 C is formed in the atmosphere and is then integrated via photosynthesis, according to a time scale of a few tens of years at most. The half-life of the 14 C is 5730 years.
  • the materials coming from photosynthesis namely plants in general, necessarily have a maximum content in isotope 14 C.
  • the determination of the content of biomaterial or of bio-carbon can be carried out in accordance with the standards ASTM D 6866-12, the method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).
  • the pressure-sensitive adhesive polymer has a content of bio-carbon of at least 10 mol-% or at least 15 mol-% or higher, e.g. 20 mol-%, 30 mol-% or 40 mol-% or higher, based on the total amount of carbon atoms in the pressure-sensitive adhesive polymer.
  • a polymer which is partly made of fully or partly biobased monomers is a polymer where not all monomers used in the polymerization are partly or fully biobased monomers.
  • a partly biobased monomer is a monomer where not all C-atoms are biobased, for example (meth)acrylic acid esters where only the acid part or only the alcohol part is biobased.
  • Suitable bio-based materials for producing the pressure-sensitive adhesive polymer are for example (meth)acrylic esters, wherein the (meth)acrylic acid component or the alcohol component or both are bio-based.
  • Suitable bio-based alcohols are for example bio-based iso-butanol, bio-based n-butanol, bio-based ethanol, bio-based iso-pentanol (3-methylbutan-1-ol), bio-based 2-octanol, bio-based 1-octanol and bio-based n-heptanol.
  • Preferred partly biobased monomers are esters of (meth)acrylic acid and bio-based alcohols, preferably bio-based 2-octanol (i) bio-based 1-octanol (v), bio-based ethanol (vii), bio-based iso-butanol (vi), bio-based n-butanol, bio-based iso-pentanol (3-methylbutan-1-ol), bio-based and bio-based n-heptanol.
  • Preferred fully biobased monomers are esters of bio-based acrylic acid and bio-based alcohols as mentioned above.
  • At least the carbon atoms of the alkyl group of at least one of the monomers 2-octyl acrylate, 1-octyl acrylate, isobutyl acrylate and ethyl acrylate is of biological origin.
  • at least 50 wt.%, more preferred 100 wt.% of 2-octyl acrylate monomer (i) is made from bio-based 2-octanol and non-bio-based or bio-based acrylic acid, i.e. preferably at least the carbon atoms of the 2-octyl group of 2-octyl acrylate (i) are of biological origin.
  • monomers (vi) comprise iso butyl acrylate wherein at least the carbon atoms of the iso butyl group are of biological origin.
  • the glass transition temperature (Tg) of the pressure-sensitive adhesive polymer is below -20°C, preferably from -50 to -25 °C.
  • T g n are the glass transition temperatures in degrees Kelvin of the polymers constructed from only one of the monomers 1, 2, .... n at a time.
  • the T g values for the homopolymers of the majority of monomers are known and are listed for example in Ullmann's Encyclopedia of Industrial Chemistry, vol. 5, vol. A21, page 169, VCH Weinheim, 1992 ; further sources for glass transition temperatures of homopolymers are, for example, J. Brandrup, E.H. Immergut, Polymer Handbook, 1st Ed., J. Wiley, New York 1966 , 2 nd Ed. J. Wiley, New York 1975, and 3 rd Ed. J. Wiley, New York 1989.
  • the polymer dispersions employed according to the invention are obtainable by free-radical emulsion polymerization of ethylenically unsaturated, free-radically polymerizable compounds (monomers).
  • the emulsion polymerization comprises polymerizing ethylenically unsaturated compounds (monomers) in water using ionic and/or nonionic emulsifiers and/or protective colloids or stabilizers as surface-active compounds to stabilize the monomer droplets and the polymer particles subsequently formed from the monomers.
  • the surface-active substances are typically used in amounts of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the monomers to be polymerized.
  • Suitable protective colloids can be found in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], volume XIV/1, Makromolekulare Stoffe [Macromolecular Materials], Georg-Thieme-Verlag, Stuttgart, 1961, p. 411 to 420 .
  • Useful emulsifiers include anionic, cationic and also nonionic emulsifiers.
  • surface-active substances it is preferable to employ emulsifiers whose molecular weight is typically below 2000 g/mol in contrast with the protective colloids. When mixtures of surface-active substances are used, the individual components must of course be compatible with one another; in case of doubt, this may be checked on the basis of a few preliminary experiments.
  • Customary accompanying emulsifiers are for example ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: C 8 to C 36 ), ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 9 ), alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C 12 to C 18 ), of ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 9 ), of alkylsulfonic acids (alkyl radical: C 12 to C 18 ) and of alkylarylsulfonic
  • R5 and R6 are hydrogen or C4- to C14-alkyl and are not simultaneously hydrogen
  • X and Y may be alkali metal ions and/or ammonium ions.
  • R5, R6 are preferably linear or branched alkyl radicals having 6 to 18 carbon atoms or hydrogen and in particular having 6, 12 and 16 carbon atoms, wherein R5 and R6 are not both simultaneously hydrogen.
  • X and Y are preferably sodium, potassium or ammonium ions, wherein sodium is particularly preferred.
  • Compounds in which X and Y are sodium, R5 is a branched alkyl radical having 12 carbon atoms and R6 is hydrogen or R5 are particularly advantageous.
  • emulsifiers for example Dowfax ® 2 A1, Emulan ® NP 50, Dextrol ® OC 50, Emulgator 825, Emulgator 825 S, Emulan ® OG, Texapon ® NSO, Nekanil ® 904 S, Lumiten ® I-RA, Lumiten ® E 3065, Disponil ® FES 77, Lutensol ® AT 18, Steinapol ® VSL, Emulphor ® NPS 25. Ionic emulsifiers or protective colloids are preferred for the present invention.
  • ionic emulsifiers in particular salts and acids, such as carboxylic acids, sulfonic acids and sulfates, sulfonates or carboxylates.
  • ionic emulsifiers in particular salts and acids, such as carboxylic acids, sulfonic acids and sulfates, sulfonates or carboxylates.
  • mixtures of ionic and nonionic emulsifiers are also employed in particular.
  • the polymerization may also be carried out in the presence of a protective colloid.
  • Protective colloids are polymeric compounds which upon solvation bind large quantities of water and are capable of stabilizing dispersions of water-insoluble polymers. In contrast to emulsifiers, they generally do not lower the interfacial surface tension between polymer particles and water.
  • the number-average molecular weight of protective colloids is above 1000 g/mol for example.
  • the emulsion polymerization may be initiated using water-soluble initiators.
  • Water-soluble initiators are for example ammonium salts and alkali metal salts of peroxodisulfuric acid, for example sodium peroxodisulfate, hydrogen peroxide or organic peroxides, for example tert-butyl hydroperoxide.
  • redox reduction-oxidation
  • Redox initiator systems consist of at least one generally inorganic or organic reducing agent and an inorganic or organic oxidizing agent.
  • the oxidizing component is, for example, the emulsion polymerization initiators already mentioned hereinabove.
  • the reductant components are for example alkali metal salts of sulfurous acid, such as for example sodium sulfite, sodium hydrogensulfite, alkali metal salts of disulfurous acid such as sodium disulfite, bisulfite addition compounds of aliphatic aldehydes and ketones, such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and the salts thereof, or ascorbic acid.
  • the redox initiator systems may be employed with co-use of soluble metal compounds whose metallic component may appear in a plurality of valence states.
  • Typical redox initiator systems are, for example, ascorbic acid/iron(II) sulfate/sodium peroxydisulfate, tert-butyl hydroperoxide/sodium disulfite, tert-butyl hydroperoxide/sodium hydroxymethanesulfinic acid.
  • the individual components for example the reductant component, may also be mixtures, for example a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the recited initiators are generally employed in the form of aqueous solutions, the lower concentration limit being determined by the amount of water acceptable in the dispersion and the upper concentration limit being determined by the solubility in water of the particular compound.
  • the concentration of the initiators is generally from 0.1 to 30 wt.%, preferably from 0.5 to 20 wt.% and more preferably from 1.0 to 10 wt.% based on the monomers to be polymerized. It is also possible to use two or more different initiators in the emulsion polymerization.
  • the polymerization may employ chain transfer agents. It is preferable when no chain transfer agents are employed. When chain transfer agents are employed they are preferably employed in amounts of at least 0.01 parts by weight of chain transfer agent per 100 parts by weight of monomers, for example of 0.01 to 5 parts by weight, or of 0.01 to 3 parts by weight, preferably of 0.01 to 0.75 parts by weight, to 100 parts by weight of the monomers to be polymerized. This makes it possible to control/reduce the molar mass of the emulsion polymer through a chain termination reaction.
  • the chain transfer agents are bonded to the polymer in this procedure, generally to the chain end. The addition may be carried out during the polymerization continuously or in stages.
  • Suitable chain transfer agents are for example organic compounds comprising sulfur in bonded form (for example compounds having a thiol group), aliphatic and/or araliphatic halogen compounds, aliphatic and/or aromatic aldehydes, unsaturated fatty acids (for example oleic acid), dienes having non-conjugated double bonds (for example divinylmethane, terpinols or vinyl cyclohexene), hydrocarbons having easily abstractable hydrogen atoms (for example toluene), organic acids or salts thereof (for example formic acid, sodium formate, ammonium formate), alcohols (for example isopropanol) and phosphorus compounds (for example sodium hypophosphite).
  • organic compounds comprising sulfur in bonded form for example compounds having a thiol group
  • aliphatic and/or araliphatic halogen compounds for example aliphatic and/or aromatic aldehydes, unsaturated fatty acids (for example oleic acid
  • the chain transfer agents are generally compounds of low molecular mass, having a molar weight of less than 2000, in particular less than 1000 g/mol. It is advantageous when a sub-amount or the total amount of the chain transfer agents is supplied to the aqueous reaction medium before initiation of the free-radical polymerization. In addition, a sub-amount or the total amount of the free-radical chain-transferring compound may advantageously also be supplied to the aqueous reaction medium together with the monomers during the polymerization.
  • Preferred organic compounds comprising sulfur in bonded form are in particular tert-butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptopropyl trimethoxysilane, tert-dodecyl mercaptan, thiodiglycol, ethyl thioethanol, di-n-butyl sulfide, 2-isopropyl sulfide, di-n-octyl sulfide, diphenyl sulfide, diisopropyl disulfide, 2-mercaptoethanol, 1,3-mercapto-propanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioacetic acid and thiourea.
  • Particularly preferred thio compounds are tert-butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptopropyl trimethoxysilane, 2-ethylhexyl thioglycolate (EHTG), isooctyl 3-mercaptopropionate (IOMPA) or tert-dodecyl mercaptan (tDMK).
  • the emulsion polymerization is generally carried out at 30°C to 130°C, preferably at 50°C to 95°C.
  • the polymerization medium may consist either only of water or of mixtures of water and liquids miscible therewith such as methanol. Preference is given to using solely water.
  • the emulsion polymerization may be carried out either as a batch process or in the form of a feed process, including the staged and gradient operating modes of a feed process. Preference is given to the feed process in which a portion of the polymerization batch is initially charged, heated to the polymerization temperature and incipiently polymerized before the remainder of the polymerization batch is supplied, typically via a plurality of spatially separate feeds, one or more of which comprise the monomers in pure form or in emulsified form, continuously, in stages or with superposition of a concentration gradient while maintaining the polymerization in the polymerization zone.
  • Seed latex is an aqueous dispersion of finely divided polymer particles having an average particle diameter of preferably 20 to 40 nm. Seed latex is used in an amount of preferably 0.01 to 0.5 parts by weight, particularly preferably of 0.03 to 0.3 parts by weight, based on 100 parts by weight of monomers. A latex based on polystyrene or based on polymethyl methacrylate is suitable for example. One preferred seed latex is polystyrene seed.
  • the manner in which the initiator is added to the polymerization vessel over the course of the free-radical aqueous emulsion polymerization is known to those of ordinary skill in the art. It may be either initially charged to the polymerization vessel in its entirety or employed continuously or in a staged manner at the rate of its consumption over the course of the free-radical aqueous emulsion polymerization. This specifically depends on the chemical nature of the initiator system and on the polymerization temperature. Preference is given to initially charging a portion and supplying the remainder to the polymerization zone at the rate of its consumption. To remove the residual monomers, initiator is typically also added after termination of the actual emulsion polymerization, i.e. after a monomer conversion of at least 95%. In the feed process, the individual components may be added to the reactor from above, from the side or from below through the reactor floor.
  • the emulsion polymerization generally affords aqueous dispersions of the polymer having solids contents of from 15% to 75% by weight, preferably from 40% to 75% by weight, particularly preferably not less than 50% by weight. Dispersions having a very high solids content are preferred for a high reactor space/time yield. In order that solids contents of >60 wt.% may be achieved, a bi- or polymodal particle size should be established since otherwise the viscosity becomes too high and the dispersion is difficult to handle. A new generation of particles may be produced, for example, by addition of seed ( EP 81083 ), by addition of excess emulsifier amounts or by addition of miniemulsions.
  • a further advantage associated with low viscosity at high solids content is improved coating characteristics at high solids contents.
  • Production of (a) new particle generation(s) may be effected at any point in time. It is guided by the particle-size distribution that is sought for a low viscosity.
  • the polymer thus produced is preferably used in the form of its aqueous dispersion.
  • the size distribution of the dispersion particles may be monomodal, bimodal or multimodal.
  • the neutralization of acid groups of the polymer is preferably carried out by feeding of a neutralizing agent during or after the polymerization, wherein the acid groups are fully or partially neutralized by feeding of a base.
  • the neutralizing agent may be added for example in a separate feed simultaneously with the feeding of the monomer mixture. After feeding of all monomers it is preferable when the amount of neutralizing agent necessary for neutralization of at least 10%, preferably from 10% to 100% or from 25% to 90%, of acid equivalents is present in the polymerization vessel.
  • a particularly preferred neutralizing agent is ammonia.
  • the pH of the polymer dispersion is preferably adjusted to a pH greater than 4.5, more particularly to a pH of between 5 and 8.
  • the pressure-sensitive adhesive composition may comprise at least one tackifier (tackifying resin).
  • a tackifier is a polymeric or oligomeric additive for adhesive polymers or generally for elastomers which increases their autoadhesion (tack, inherent tack, self-adhesion) so that after short, light contact pressure they adhere to surfaces firmly.
  • Tackifiers include for example natural resins, such as colophony resins and the derivatives thereof formed by disproportionation or isomerization, polymerization, dimerization or hydrogenation or terpene resins. These may be in their salt form (with for example monovalent or polyvalent counterions (cations)) or preferably in their esterified form. Alcohols used for esterification may be monohydric or polyhydric.
  • tackifying resins examples include methanol, ethanediol, diethylene glycol, triethylene glycol, 1,2,3-propanethiol, pentaerythritol.
  • hydrocarbon resins for example coumarone-indene resins, polyterpene resins, hydrocarbon resins based on unsaturated CH compounds, such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, alpha-methylstyrene, vinyltoluene.
  • Tackifiers are known for example from Adhesive Age, July 1987, pages 19-23 or Polym. Mater. Sci. Eng. 61 (1989), pages 588-592 .
  • Polyacrylates having a low molar weight can also be used as tackifiers. These polyacrylates preferably have a weight-average molecular weight M w less than 50 000, in particular less than 30 000.
  • the tackifying polyacrylates preferably consist to an extent of at least 60% by weight, in particular at least 80% by weight, of C 1 -C 8 alkyl (meth)acrylates.
  • Suitable tackifiers include for example the low-molecular-weight polymers and oligomers described in WO 2013/117428 having a weight-average molecular weight of less than 50 000 and a glass transition temperature of not less than -40°C to not more than 0°C, preferably of not less than -35°C to not more than 0°C, producible by emulsion polymerization in the presence of at least one molecular weight regulator and producible from a monomer mixture comprising at least 40% by weight of at least one C1- to C20-alkyl (meth)acrylate.
  • Preferred tackifiers are selected from the group consisting of natural resins, hydrocarbon resins, tackifying polyacrylates or mixtures thereof.
  • Particularly preferred tackifiers include natural or chemically modified colophony resins. Colophony resins consist predominantly of abietic acid or abietic acid derivatives or hydrogenated derivatives thereof.
  • the tackifiers may be added to the polymer dispersion in simple fashion.
  • the tackifiers themselves are preferably in the form of an aqueous dispersion.
  • the amount by weight of the tackifiers is preferably 5 to 100 parts by weight, particularly preferably, 5 to 50, 5 to 40, or 10 to 40 parts by weight, based on 100 parts by weight of polymer (solid/solid).
  • Most preferred are tackifiers of biological origin such as natural resins, including chemically modified natural resins-
  • the pressure-sensitive adhesive composition may comprise further additives, for example fillers, dyes, leveling agents, flow control assistants, thickeners (preferably associative thickeners, more preferably associative polyurethane thickeners), defoamers, crosslinkers, plasticizers, pigments, UV protectants, biocides, dispersing aids or wetting agents.
  • the pressure-sensitive adhesives may include in particular wetting auxiliaries (wetting agents), for example fatty alcohol ethoxylates, alkylphenol ethoxylates, sulfosuccinic esters, nonylphenol ethoxylates, polyoxyethylene/polyoxypropylene copolymers or sodium dodecyl-sulfonates.
  • Defoaming agents are oil-based defoamers, water-based defoamers or silicone-based defoamers.
  • Oil based defoamers have an oil carrier.
  • the oil might be mineral oil, vegetable oil, white oil or any other oil that is insoluble in the foaming medium.
  • An oil based defoamer also contains a wax and/or hydrophobic silica to boost the performance.
  • Typical waxes are ethylene bis-stearamide (EBS), paraffin waxes, ester waxes and fatty alcohol waxes. These products might also have surfactants to improve emulsification and spreading in the foaming medium.
  • Preferred defoaming agents are silicone oils, hydrophobized silica particles, wax particles, natural fatty acid oils and paraffins (preferably aromatics-free white oils).
  • Water based defoamers are oils and waxes dispersed in a water base.
  • the oils can be mineral oil or vegetable oils and the waxes can be fatty alcohols, fatty acid soaps or fatty acid esters.
  • Silicone-based defoamers are polymers with silicon backbones such as polydimethylsiloxane. These might be delivered as an oil or a water based emulsion.
  • the silicone compound can consist of a hydrophobic silica dispersed in a silicone oil. Emulsifiers are added to ensure that the silicone spreads fast and well in the foaming medium.
  • the silicone compound might also contain silicone glycols and other modified silicone fluids.
  • EO/PO based defoamers contain polyethylene glycol and polypropylene glycol copolymers. They are delivered as oils, water solutions, or water based emulsions. EO/PO copolymers normally have good dispersing properties and are often well suited when deposit problems are an issue.
  • the amount of additives is preferably 0.05 to 10 parts by weight, 0.1 to 5 parts by weight, especially 0.1 to 3 parts by weight, per 100 parts by weight of adhesive polymer (solid).
  • a tackified pressure-sensitive adhesive composition preferably comprises (based on solids)
  • a non-tackified pressure-sensitive adhesive composition preferably comprises (based on solids)
  • the pressure-sensitive adhesive composition is preferably a one-component pressure-sensitive adhesive.
  • One-component adhesives are adhesives to which no external crosslinking agent (for example isocyanate crosslinker) is added immediately before use.
  • the pressure-sensitive adhesive composition forms a film having a tack of preferably not less than 7 N/25 mm measured as loop tack relative to a polished steel surface or relative to a polyethylene surface (adhesive applied at an application rate of 17 g/m 2 on a 70 g/m 2 paper (HERMA Etikettenpapier)), measured relative to steel or a polyethylene surface at 23°C and 50% relative humidity at a tear-off speed of 300 mm/min (see examples for details).
  • the pressure-sensitive adhesive composition forms a film having a peel strength of preferably greater than 2 N/25 mm relative to a polyethylene surface (measured at an application rate of 17 g/m 2 on a 70 g/m 2 paper (HERMA Etikettenpapier) measured relative to polyethylene at 23°C and 50% relative humidity at a tear-off speed of 300 mm/min, see examples for details) and more than 7 N relative to a polished steel or a glass plate.
  • HERMA Etikettenpapier measured relative to polyethylene at 23°C and 50% relative humidity at a tear-off speed of 300 mm/min, see examples for details
  • the pressure-sensitive adhesive composition After drying, the pressure-sensitive adhesive composition forms a film having a shear resistance at 23°C of preferably at least 300 minutes, measured as described in the examples.
  • the pressure-sensitive adhesive composition may be used to produce self-adhesive articles.
  • the articles are at least partially coated with the pressure-sensitive adhesive.
  • the self-adhesive articles may be self-adhesive labels, self-adhesive tapes or self-adhesive films including graphic films and protective films. Suitable carrier materials are for example paper, plastic films and metal foils.
  • the inventive self-adhesive tapes may be tapes of the above mentioned substances coated on one or both sides.
  • the inventive self-adhesive labels may be labels made of paper or a thermoplastic film. Adhesive tapes made of thermoplastic film are particularly preferred.
  • thermoplastic films include for example films made of polyolefins (for example polyethylene or polypropylene), polyolefin copolymers, films made of polyesters (for example polyethylene terephthalate), polyvinyl chloride or polyacetate.
  • the surfaces of the thermoplastic polymer films have preferably been corona-treated. Foamed carriers are also possible.
  • the labels have been coated with adhesive on one side.
  • Preferred substrates for the self-adhesive articles are paper and polymer films.
  • the self-adhesive articles have been at least partially coated with a pressure-sensitive adhesive according to the invention on at least one surface.
  • the adhesive may be applied to the articles by customary methods such as roller application, knife coating or spreading.
  • the application rate is preferably 0.1 to 300 g, more preferably 2 to 150 g of solid per m 2 .
  • Application is generally followed by a drying step for removal of the water.
  • the water may be removed by drying at 50°C to 150°C for example.
  • the thus obtained coated substrates are used for example as self-adhesive articles, such as adhesive labels, adhesive tapes or adhesive films. To this end the carriers may be cut into adhesive tapes, labels or films before or after application of the adhesive.
  • the side of the substrates coated with pressure-sensitive adhesive may be covered with a release paper, for example with a siliconized paper, for later use.
  • the substrates to which the self-adhesive articles may advantageously be applied may be metal, wood, glass, paper or plastic for example.
  • the self-adhesive articles are especially suitable for bonding to packaging surfaces, cardboard boxes, plastic packaging, books, windows, vapor barriers, motor vehicle bodies, tires or vehicle body parts.
  • the invention further relates to the use of the pressure-sensitive adhesive composition described hereinabove for producing self-adhesive labels, self-adhesive tapes or self-adhesive films.
  • the invention further relates to self-adhesive articles coated with a pressure-sensitive adhesive composition described hereinabove.
  • the invention further relates to a process for producing a self-adhesive article.
  • the process comprises the steps of
  • the emulsion feed is prepared by mixing the monomers listed in table 1 with water, 1.1 pphm of emulsifier Disponil ® FES 77 and 0.2 pphm of emulsifier Dowfax ® 2A1 as well as 0.2 pphm of sodium hydroxide.
  • a reactor equipped with stirrer, temperature control and several injection possibilities, is charged with water, 0.05 pphm ascorbic acid and heated to 85 °C (C1: 90 °C). 0.11 pphm of sodium persulfate as initiator is added and the emulsion feed is started simultaneously with a feed of 0.25 pphm sodium persulfate for 195 minutes (C1: 270 minutes).
  • the emulsion feed is prepared by mixing the monomers listed in table 1 with water, 1.32 pphm of emulsifier Disponil ® FES 77, 0.18 pphm of emulsifier Dowfax ® 2A1 and 0.4 pphm Lumiten ® I-SC.
  • a reactor equipped with stirrer, temperature control and several injection possibilities, is charged with water and 0.08 pphm polystyrene seed and heated to 85 °C. 0.04 pphm of sodium persulfate as initiator is added and the emulsion feed is started simultaneously with a feed of 0.53 pphm sodium persulfate for 210 minutes.
  • Table 1a Monomer compositions of pressure-sensitive adhesive polymer dispersions; amounts in parts by weight E1 E2 E3 E4 C1 C2 C3 C4 1) C5 2) C6 2) C7 3) Bio-2-OA 64.5 79.5 80 53 91.5 90.5 92.5 1-OA 10 i-BA 5 EA 20 2-EHA 8 23 79,5 87,5 87,5 86.5 MMA 8 8 2 2 2 10 10 10 9 MA 2 2 8 S 2 1 1 1 2 1 1 VAc 8 8 5 5 5 5 8 2 HPA 2 2 2 2 2 1 1 2 AA 0.5 0.5 1 1 0.5 0.5 0.5 0.5 0.5 0.5 Tg -31 -31 -41 -41 -40 -41 -41 -40 -46 -46 -46 1) according to example E7 of WO 00/68335 2) according to example E1 of WO 00/68335 3) according to example E2 of WO 00/68335 Table 1b: Monomer compositions of pressure-sensitive adhesive polymer dispersions;
  • Examples labelled C are comparative examples, examples labelled E are inventive examples. Compared to the comparative examples, 2-EHA, and in some examples MMA and VAc are replaced by sufficient amounts of bio 2-OA and in some examples bio 1-OA , bio-IBA and bio-EA so as to result in polymers according to the invention with similar glass transition temperature.
  • the pressure-sensitive adhesives of examples E3 to E4 and C6 and C7 are coated with a coating weight of about 17 g/m 2 (dried film) onto an 40 ⁇ m strong oriented polypropylene (oPP) film as the carrier and dried for 3 minutes at 90°C.
  • the pressure-sensitive adhesives of examples E1 to E2 (not including tackifier) and E5 (including tackifier) as well as C1 to C5 are coated at an application rate of about 17 g/m 2 (dried film) onto siliconized release paper and dried 3 min at 90°C.
  • the dried adhesive polymer films are then transferred onto label paper facestock material (HERMA Etikettenpapier 70 g/m 2 non-primered).
  • the substrates coated with adhesive are stored for 24 h under standard conditions, before the adhesive properties are determined under standard conditions (SC: 23°C, 50% relative humidity).
  • Loop tack (quick stick, corresponding to FINAT test method FTM9)
  • Determining loop tack (also known as surface tack or quick stick) comprises determining the force required for removal from a substrate of an adhesive applied to a carrier material by pressureless adhesive bonding onto the substrate at a defined tear-off speed, measured at 23°C and 50% relative humidity.
  • Test substrates are polished stainless steel, HDPE or glass.
  • a test strip of 25 mm in width and 250 mm in length is cut from the carrier coated with adhesive and stored for at least 16 hours at SC. Both ends of the test strip are folded over to about 1 cm in length with the adhesive side facing inward. The adhesive strip is used to form a loop with the adhesive side facing outward, and the two ends are brought together and clamped into the upper jaw of a tensile testing machine.
  • test substrate holder is clamped into the lower jaw.
  • the adhesive strip loop is moved downward by the tensile testing machine at a speed of 300 mm/minute, thus bonding the adhesive side of the test strip to the substrate without additional pressure.
  • the tensile testing machine is halted and immediately moved upward again when the bottom edge of the upper jaw is 40 mm above the substrate.
  • the test result is reported in N/25 mm width.
  • the maximum value on the display (Fmax) is read off as the measure of surface tack. An average of three individual results is taken.
  • Peel strength is a measure of adhesion measured at 23°C and 50% relative humidity. In the determination of peel strength a 25 mm wide test strip is in each case bonded to a test specimen made of HDPE, polished stainless steel or glass and rolled twice with a 2 kg roller (diameter 85 mm, Shore hardness 80A). One end is then clamped in the upper jaws of a tensile strain tester. The adhesive strip is removed from the test surface at 300 mm/min at an angle of 180°, i.e. the adhesive strip is bent and removed parallel to the test specimen and the force required therefor is measured. The measure for peel strength is the force in N/25 mm obtained as the average value from five measurements. The peel strength was determined 24 hours after bonding. The adhesive strength has fully developed after this time. An average of three individual results is taken.
  • Self-adhesive paper labels If the peel strength extends a certain threshold, a break of the paper carrier material is observed. In such a case the tensile strain is not a meaningful result and "paper tear" is indicated instead.
  • Shear strength is a measure of cohesion measured at SC.
  • the carrier coated with pressure-sensitive adhesive is cut into test strips of 25 mm or 12.5 mm in width.
  • the measure of shear strength is the time in hours until the weight falls off; the average of 3 measurements is taken in each case.
  • examples show that examples with polymers comprising bio-based 2-octyl acrylate units instead of 2-ethylhexyl acrylate units (E3, E4 compared to C6 and C7) result in improved shear strength (high cohesion) and sufficient tack and peel strength (adhesion) when used for filmic labels.
  • the examples show that copolymerizing 1-2 parts per weight each of styrene and hydroxyalkyl acrylate is particularly beneficial for an optimum balance of shear and peel resistance, in particular for improved shear strength when used for paper labels (E1, E2 compared to C1 to C3).
  • the examples show that examples with polymers comprising bio-based 2-octyl acrylate units instead of 2-ethylhexyl acrylate units (E1, E2 compared to C4 and C5) result in improved shear strength (high cohesion) and improved peel strength (adhesion) when used for paper labels.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP22195431.6A 2022-09-13 2022-09-13 Procédé pour la préparation d'un polymère adhésif sensible à la pression dispersé Withdrawn EP4155330A1 (fr)

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EP22195431.6A EP4155330A1 (fr) 2022-09-13 2022-09-13 Procédé pour la préparation d'un polymère adhésif sensible à la pression dispersé
PCT/EP2023/074434 WO2024056484A1 (fr) 2022-09-13 2023-09-06 Composition adhésive sensible à la pression comprenant un polymère adhésif sensible à la pression dispersé, constitué par polymérisation en émulsion d'acrylate de 2-octyle, de styrène, d'acrylate d'hydroxyalkyle, de monomères présentant au moins un groupe acide en quantités spécifiques et éventuellement d'autres monomères.

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000068335A1 (fr) 1999-05-06 2000-11-16 Basf Aktiengesellschaft Adhesifs de contact
EP1342762A2 (fr) * 2002-03-07 2003-09-10 Basf Corporation Dispersion a haute teneur en solides pour des adhesifs qui sont sensibles a la pression et qui sont utilisables dans une large gamme de temperatures
WO2009129087A1 (fr) 2008-04-14 2009-10-22 3M Innovative Properties Company Composition adhésive de (méth)acrylate de 2-octyle
EP2626397A1 (fr) 2012-02-09 2013-08-14 tesa AG Bandes adhésives à base de monomère bio
WO2013117428A1 (fr) 2012-02-06 2013-08-15 Basf Se Dispersion polymère aqueuse pouvant s'utiliser comme agent poisseux pour adhésifs, obtenue par polymérisation en émulsion à base d'acryl(méth)acrylates c1 à c20
US20160002140A1 (en) * 2013-03-15 2016-01-07 3M Innovative Properties Company Selective synthesis of 2-octyl acrylate by acid catalyzed esterification of 2-octanol and acrylic acid
US20200017725A1 (en) 2017-02-03 2020-01-16 Synthomer Usa Llc Pressure Sensitive Adhesive Compositions and Methods for Preparing Same
WO2022034247A1 (fr) * 2020-08-14 2022-02-17 Tesa Se Adhésif sensible à la pression

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000068335A1 (fr) 1999-05-06 2000-11-16 Basf Aktiengesellschaft Adhesifs de contact
US6620870B1 (en) * 1999-05-06 2003-09-16 Basf Aktiengesellschaft Contact bonding adhesives
EP1342762A2 (fr) * 2002-03-07 2003-09-10 Basf Corporation Dispersion a haute teneur en solides pour des adhesifs qui sont sensibles a la pression et qui sont utilisables dans une large gamme de temperatures
WO2009129087A1 (fr) 2008-04-14 2009-10-22 3M Innovative Properties Company Composition adhésive de (méth)acrylate de 2-octyle
WO2013117428A1 (fr) 2012-02-06 2013-08-15 Basf Se Dispersion polymère aqueuse pouvant s'utiliser comme agent poisseux pour adhésifs, obtenue par polymérisation en émulsion à base d'acryl(méth)acrylates c1 à c20
EP2626397A1 (fr) 2012-02-09 2013-08-14 tesa AG Bandes adhésives à base de monomère bio
US20160002140A1 (en) * 2013-03-15 2016-01-07 3M Innovative Properties Company Selective synthesis of 2-octyl acrylate by acid catalyzed esterification of 2-octanol and acrylic acid
US20200017725A1 (en) 2017-02-03 2020-01-16 Synthomer Usa Llc Pressure Sensitive Adhesive Compositions and Methods for Preparing Same
WO2022034247A1 (fr) * 2020-08-14 2022-02-17 Tesa Se Adhésif sensible à la pression

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J. BRANDRUPE.H. IMMERGUT: "Polymer Handbook", 1966, J. WILEY
POLYM. MATER. SCI. ENG., vol. 61, 1989, pages 588 - 592
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